Bonded glass fiber product and method of making same



Sept. 13, 1955 L. P. Biz-:FELD ErAL 2,717,841

SS FIBER PRODUCT AND METHOD OF' MAKING SAME BONDED GLA Filed Jan. 9, 1951 BONDED GLASS FIBER lPRODUCT ANDME'ITHOD Lawrence P. Biefeld, Granville,

F MAKING ySAME Marshall C. Armstrong,

Hebron, and Richard F. Shannon, Lancaster, Ohio, as-

signors to -Gwens-Corning'Fiberglas ledu, Ohio, a

` Corporation, Iocorporation of Delaware Application Janualyrf, 195 1, Serial No. 205,132 14 Claims. (Cl. 117-102) This invention and boards based upon organic cement and which relates to the manufacture of panels glass fibers bonded with an inis characterized by hardness,

strength and by porosity throughout to enable use of the board as insulat structural board a Organic resino i011, Lith, n d the like, us vbinders have, in the past, been used roof decking, heat barriers,

in the manufacture of glass fiber reinforced structural and insulation board but does incorporation of not enable Agreatest benefits to such usage of organicbinders be derived from the This is because (1) the i glass fibers.

`temperature limitation of the `organic rbinderis imposed upon the h eat resistant glass fibers and `such limitations are controliing'in the L giauszs fiber reinforced product, (2)

the organic binder is 'subject to combustion whereas one of the most desirable properties Vtha't'fiow f r c :n 1` glass fibers lis their in ertness and non-inammability, 3) `or- Structural Y boards andthe relatively high cost of the binder prohibits e such end produc @magasinageof difficult to maintain strong .adherente .beweerde greenisbiadef @@Ui glass 'ber surfaces, especially under humidity conditions, so that maximum bentft Qwest readily be derived fram such combination The needin `.the structural `s ulatitm is to ha s of rn aterials.

tield andin the .field of inve a substantiallyLcompletely` inorganic board which islhardLdeiiseand ofhighstrength yet has `suieient:pt )rrousity,for purposesvof insulation and to ,enable :breathiils described is prefeiably selected `,of of their high strength ture, rot, fungus .The ber: Das@ tot a. board, of th Ytyre giass .fibers because andA resistance towheat, flame, moisavttack and the like, butAthe problem `which, prevails in therauseisthe .manufacture ofsuch a fiber glass board with any characteristics.

inorganic binder4 to embody such A large. number of inorganic .cements, .such as gypsum,

Portland cement,

have been tried.

magnesium @X3/Sulphate Yand the like, It ispreferred to adapt magnesium oxychloride or magnesium .oxysulphate for such usage because (l) s lurries can be.

relatively high stage does not a of the` glass fibers. or the ysur their properties,

.cement content, (2) the lrelatively` light` weightbut .of elasticity, (4) ,the .cement in formed. thereof` `which have a cured cement s (3) ,ithas lpwmodulus the' .c ured .or uncured orV otherwise. affect vthe properties e'sthereofsuch `as ltol alter (5) it hashigh vvater.ofecrystallization .sffenltpresentrd Ain Strong,

the elimination of aqueous ydiluent;in lan,,applied binder temperatures even 119.011-, lang the cement `is relatively t stable to high and continuous exposure,

and 67,) the,v .cemenn system isamenableito curemwith heat and the raw materials of which it is formed are readily available.

.sement liadeltfo glass'. fiber; pautas las satisfied.. baut sulphate cement,

' .Pian

ephedrine features 'plied ,fo Hd .to pretreatmllt .0f v the glass gesuiti.

y,mass and `characterized to facilitate rapid .and and oiutof the interstices lheat .inV heffecting pliate cement may ,alcined brucite', such .riyedfrom'the brineV [to: be"compared to the relatively Patented Sept. 13, 1955 ice 2 the difficulty Vof incorporating or applying the binder composition onto the glassiibers as they are formed to achieve uniform binder distribution and well bonded libers Some of the diculty may be Vtraceable Ato the ,lack of plastic ilovv of the bin-der during the curing cycle materials during an equivalent stage ot' Responsibility for the inability to dehseslsd entering into the interior of the body for reaction in cement formation. i Y

.It is .ambita @.f this .inventan t0 Produce @13d t9 PrO- ture, which provides for uniform distributionofthe binder throughout the end product, which ei'iarble's`- the 4use-of and accelerating cure, which can be eirpgsed to lrelatively lhigh temperatures ,for long 'periods ,of time without floss of strength or contour,'which'V is flame-proof, which is ,porouslwhch permits variation of the 4glass yfiber to cement ratio ,over 'affairly 'widellrange which provides densities ranging,frorn`1535pounds per cubic foot. while.stillmaintaining,highporosity, and which is ayiiowsheet tice of this invention, and

rl"`igt 1re 2 is a scctionalelevational View through aboard of this inventionfh lt `has"be`en found that manufacture of astructural board :offglass iibers bondedfv/it'ha' magnesiuiri oxysiil- A be*suceessfullypracticed vvheii tan eX- c :essv of "the vcement slurry is incorporatedy or appiiedfto ropposite,the side upronvvhi'ch" the slurry* irstiap- ASuccessful practice of thisv technique has vbeerl depend Vgreatly upon factors, which include proper A f ber, Surfaces .to .encourage .rapid v vjettmg out of Ythen'fslurryfvvithou't 4channeling.fand pioper u ipn `of the slurry, such as the use ofcalcineidmag- `oride` of mostfavorable particle sitze and lshape Ytfomilitateagainsty ltering o ut onfthe surface ofthe by highbulk density-but 10W .viscosity to favor 110W into theglassvbermass, and also ,the incorporation of proper `wetting agents into the slurries uniformlflQW of the `slurryinto of themass. 'l

lest ,usel in the practice of this nvention is made of Vas ca lcin'ed magnesium oxide deat Luddin'gton, ,Michigan `This is unsuccessful use of calclned Vmagnesium `oxidederived `frornsea Water ormost natural sources. The dierencesinlmagnesiumoxide,

which may be controlling in lthe delnitionlf theus'ability one and the unusabiltytof thefother, may b able to `the` structure particles. Calcined brucite from Luddington brine exists in the form of rounded particles having substantially little variation in particle size which averages about -12 microns, while calcined magnesium oxide derived from sea water is composed of odd shaped particles having an average particle size of about 2-3 microns but some of the particles are very large and others very small. The bulk density of calcined brucite from Luddington brine is around 55 pounds per cubic foot while calcined magnesium oxide derived from sea water has a bulk density of 30-35 pounds per cubic foot. The latter has a much higher viscosity in equivalent amounts of water. It is possible that this greater viscosity is an important factor in the ability properly to make use of a slurry based upon such calcined magnesium oxide particles.

It is believed that a solid solution forms as the calcined magnesium oxide enters into solution in the magnesium sulphate solution. High strength properties are achieved when 1.5-3 parts calcined magnesium oxide (MgO) are combined with 3 parts by weight magnesium sulphate (MgSOiJI-IaO) (3-6 mols MgO to l mol MgSO4-7H2O). Optimum conditions exist when the materials are present in the ratio of about 4.5 niols MgO to l mol MgSO4.7H2O. When magnesium sulphate is used in amounts less than per cent by weight of the binder, the magnesium oxide tends to hydrate to unreactive magnesium hydroxide instead of entering into the solid solution and a very weak cement product results.

The glass fiber component is usually first formed into a mass, such as a matt or batt, for receiving excess of the cement slurry, portions of which are subsequently drawn off to leave the desired amount uniformly distributed throughout the glass fiber mass. The mass may be in the form of a bonded matt of glass fibers having l-l0 percent by weight of a heat hardenable resinous material as the bonding agent, such as phenol formaldehyde, urea formaldehyde, furfuryl alcohol resin, melamine formaldehyde, butadiene acrylonitrile copolymer resin or the like. Instead, the mass may be formed of unbonded glass wool fibers felted upon forming into a highly porous layer. It is possible also to replace the glass fibers in whole or in part with continuous fibers or strands of substantial length or cut to shorter lengths for the purpose of imparting greater strength to the board.

There are a number of surface active or wetting agents which may be used to assist penetration and wetting out of the glass fibers by the slurry. Some have been found to be better than others under certain conditions and in particular environments. For example, with glass fibers integrated into a mass with a phenol formaldehyde resin, best use is made of wetting agents selected from the group consisting of alkyl, aryl and mixed alkyl-aryl sulfonates and alkali metal salts thereof, such as sulfonated fatty esters, alkyl aryl ether sulfates, sodium alkyl sul- 7 fonate, sodium alkyl aryl sulfonate, sodium alkyl naphthalene sulfonate, sodium lauryl sulphate, sodium monosulfonate of butyl phenyl phenol and the like, fatty acid amines and esters including sorbitan sesquioleate, trioleate of sorbitan polyoxyethylene and the like, and ethers such as alkyl aryl polyethylene glycol ether and polyglycol esters. With white wool glass fibers free of resinous binder, best use may be made of alkyl and aryl and mixed alkyl aryl sulfonates and the water soluble salts thereof, such as alcohol sulphates, sodium salts of alkyl naphthalene sulfonic acid, sodium alkyl sulfonate, sodium salt of alkylated aryl polyether sulpliates and the like, fatty acid esters of higher alcohols including ethylene oxide condensate of fatty acids, trioleate of sorbitan polyoxyethylene derivative, sorbitan monostearte polyoxyethylene derivative and the like. Although the full complement of wetting or surface acting agent may be incorporated into the slurry to aid in wetting out of the slurry, it is best if the glass fiber mass is first treated with wetting agent, while some of the same or another wetting agent is also incorporated in the slurry composition.

For practical reasons, it is best to maintain the con centration of wetting agent as low as possible. For pretreatment of the glass fibers, concentrations ranging from 0.05-l.0 percent may be used while, in the slurry, the concentration may range from 0.05-2 percent by weight. In some instances it is best to use one surface active agent for prewetting the fibers and another as a part of the slurry-the former being selected to be more receptive to the glass fiber surfaces for the purpose of modifying the characteristics thereof. The introduction of wetting agent into the slurry in some instances appears to cause thickening of the slurry but such thickening has little iniiuence upon the improvement which results in the penetrating power and the elimination of channeling and separation of particles. The following is illustrative of the practice of this invention:

Example I A glass fiber layer having a density of about 7 pounds per cubic foot, formed of wool fibers bonded with phenol formaldehyde resin, is prewet with a 0.5 percent solution of the sodium salt of alkyl naphthalene sulfonic acid (wetting agent). A slurry composed of 100 parts by weight calcined brucite, 150 parts by weight water, 150 parts by weight magnesium sulphate (MgSOMHzO) and 1.25 parts by weight sodium salt of alkyl naphthalene sulfonic acid is homogenized in a mixer and fed down a sluiceway onto the surface of the bonded glass fiber layer as it travels in one direction. The amount of slurry fed onto the surface of the layer is in excess of that desired to be retained in the board, yet under the conditions existing, the slurry rapidly disappears into the mass without separation of particles on the surface thereof. The layer is then passed over a suction chamber which withdraws slurry over and above the amount that is desired to have remain in the board. By proper regulation of suction and duration thereof, as well as by formulation of the slurry, the amount of binder that remains and the porosity, hardness and density of the board can be easily controlled.

ln the practice of this invention, boards having a density in excess of l5 pounds per cubic foot are produced ranging on up to hard, rock-like, though porous boards having a density of -35 pounds per cubic foot. As the ratio of fiber to cement approaches that deemed necessary to give density of pounds per cubic foot, the porosity begins rapidly to fall off and therefore ratios of about 4 parts glass fibers to 24 parts cement (about 30 pound board) forms the upper limit of concentration while about l part by weight fibers to 1.5 parts by weight cement supplies the lower limit of concentration.

in the above illustration the board is moved at a rate of about 6 feet per minute and the slurry disappears from the surface before the board has traveled 2 inches. After suction to remove excess slurry, the board was dried for 1 2 hours at 240 F. The product had a density of 18-20 pounds per cubic foot and was hard and porous.

Example 2 A batt formed of white glass wool fibers is prewet with a 0.3 percent aqueous solution of a fatty acid ester of a higher polyalcohol wetting agent. A slurry is formed of parts by weight calcined brucite, 100 parts by weight magnesium sulphate (MgSO4.7H2O), 150 parts by weight water and 2 parts by weight ethylene oxide condensate of oleic acid. Excess slurry is applied onto the upper surface of the batt and the excess is sucked olf from the under side as the batt later passes over a suction chamber. Air drying is possible to produce the end product, but drying time and cure can be accelerated by exposure to elevated temperatures in the range of 20G-350 F.

Example 3 A slurry formed of parts by weight calcined brucite, 300 parts by weight magnesium sulphate (MgSOiJHzO), 200 parts by weight water and 2 parts by weight sorbitan excess tonto the surface monostearate polyoxyethylene derivative applied in lof la glass -wool batt having a density of about pounds per: cubic foot. Suction is apin excess of :that :necessary V.to maintain a ratio of l part by #weight glass bers `to 2 parts by weight dry cement. When dried, the product is hard and porous and weighs about l5 pounds per cubic foot.

lt is undesirable to use more than a 2 to 1 ratio of water to calcined magnesium oxide while optimum vresu'lts are secured when .theratio is l tto f1 ,or less rwit'hin `the limitation necessary to supply the 4combined water .and water Vof reaction.

jIt will `be apparent from the description that we have .provided a :new and improved porous board ,product suitable for structural boards where either insulation, heat, ame, strength and hardness or .any-combination of such elements are important factors. The rproductof this invention is based chiefly `onglass bers fbonded with magnesium .oxysnlphate Vor .oxychloride Acements .uniformly distributed throughout the mass in a manner which .has qheretofore not been attainable by the industry and we have provided a new and improved method for manufacturing same.

It will be understood that numerous changes may be made in composition, method of application and apparatus within the scope of the invention without departing from the spirit of the invention, especially as dened in the following claims.

We claim:

1. An article of manufacture comprising a porous, hard, board-like member consisting essentially of glass bers bonded with an inorganic cement selected from the group consisting of magnesium oxychloride and magnesium oxysnlphate and present in the ratio of 1 part by weight glass bers to 1.5-6 parts by weight cement.

2. An article of manufacture comprising a porous, board-like member consisting essentially of glass bers bonded with a magnesium oxysulphate cement having calcined brucite as the magnesium oxide component thereparts by weight magnesium oxide to 3 parts by weight magnesium sulphate and present in the ratio of 1 part by weight glass bers to 1.5-6 parts by weight cement the porous, board-like member having a density ranging from 15-35 pounds per cubic foot.

3. An article of manufacture comprising a porous, hard, board-like member consisting essentially of glass fibers bonded with a magnesium oxysnlphate cement formulated of calcined magnesium oxide in the form of round particles having a uniform size averaging about 10-12 microns and a bulk density of S5 pounds per cubic foot and magnesium sulphate (MgSO4.7H2O) in the ratio of 1.5-3 parts by weight calcined magnesium oxide to 3 parts by Weight magnesium sulphate and with the cement being present in an amount ranging from 1.5-6 parts by Weight cement to 1 part by weight glass bers.

4. An article of manufacture as claimed in 2 in which the glass bers are coated with a wetting agent and in which the cement has 0.05-2.0 percent wetting agent.

5. The method of manufacturing a porous structural board comprising the steps of applying a slurry of a cement composition selected of the group consisting of magnesium oxychloride and magnesium oxysnlphate in excess of an amount that it is desired to have remain in the board onto one Wall of a porous glass ber mass, drawing off the slurry in excess of that to provide 1.5-6 parts by weight cement to one part by weight glass ber through an opposite wall, and then setting the cement that remains distributed with the glass bers.

6. The method of manufacturing a porous structural board comprising the steps of preparing a cement slurry of magnesium oxysnlphate formed of ingredients present in the ratio of 1.5-3 parts by Weight calcined magnesium oxide to 3 parts by weight magnesium sulphate and in which the calcined magnesium oxide component is vglycol `ethers, rpolyglycol esters, l .alcohols ,and ethylene oxide Condensates Vof 4fat-ty acids,

`and then drying ,the product to set Vthe cement.

7. The method of manufacturing -a glass ber reinforced, porous structural lboard comprising the steps of preparing an aqueous slurry of 1.5-3 parts ,by .weight .calcined .brucite having a narrow particle size distribution irange averaging 4about v1.0-12 microns to 3 parts by weight magnesium sulphate (MgSOiil-n) and ya wettingagent selected Vfromthe group consisting of alkyl, aryl and mixed alkyl aryl sulfonates, and alkali metal -salts thereof, fatty acid amines, fatty acid esters, polyfatty acid esters .Qf .bisher applying the `vslurry Aonto fa fibrous alessia-venin excess ,of the amount of cement that it is A desired ,to havegemain inthe tna1.-pr0duct,-whieh ranges from -1 12a-rt by weight falassnbers to 1.5-6 parts :by weight sement, drawing 01T the excess slurry from the under side of the n iass, and heating the board to drive oif the diluent and set the cement.

8. The method of manufacturing a glass ber reinforced porous structural board comprising the steps of preparing a slurry of calcined brucite and magnesium sulphate (MgSO4.7H2O) and a wetting agent in amounts ranging from 1.5 3 parts by weight calcined brucite to 3 parts by Weight magnesium sulphate and 0.05-2 percent wetting agent, applying the slurry onto a fibrous glass layer in excess of the amount of the cement that it is desired to have remain in the product which ranges from 1 part by weight glass bers to 1.5-6 parts by weight cement, drawing off the excess slurry from the under side of the glass ber mass and drying the product to set the cement.

9. The method of manufacturing a glass ber reinforced porous structural board comprising the steps of preparing an aqueous slurry of calcined brucite and magnesium sulphate (MgSO4.7H2O) in amounts ranging from 1.5-3 parts by weight calcined brucite to 3 parts by weight magnesium sulphate and 0.05-2 percent wetting agent, prewetting a glass ber mass with a wetting agent, applying the slurry onto one surface of the prewet glass ber mass in excess of the amount of the cement that it is desired to have remain in the nal product, sucking off the cement in excess of the amount to provide 1.5-6 parts by weight cement to one part by weight glass bers from the opposite side of the mass, and drying the product to set the cement.

l0. The method as claimed in claim 8 in which the glass ber layer onto which the slurry is applied is bonded with a phenol formaldehyde resin and the wetting agent is a compound selected from the group consisting of alkyl sulfonates, aryl sulfonates, alkyl aryl sulfonates and water soluble salts thereof.

11. An article of manufacture comprising a porous, board-like member consisting essentially of glass bers bonded with a magnesium oxysnlphate cement formed of calcined brucite having a narrow particle size distribution range averaging about 10-12 microns and present in the ratio of 1.5-3 parts by weight calcined brucite to 1-3 parts by weight magnesium sulphate, and present in the ratio of 1 part by weight glass bers to 1.5-6 parts by weight cement.

l2. An article of manufacture comprising a porous, board-like member consisting essentially of glass bers bonded with a magnesium oxysulphate cement containing a wetting agent selected from the group consisting of alkyl, aryl, and mixed alkyl aryl sulfonates, and alkali metal salts thereof, fatty acid amines, fatty acid esters, polyglycol ethers, polyglycol esters, fatty acid esters of higher alcohols and ethylene oxide condensates `rounded particles having a narrow of fatty acids, the magnesium oxysulphate cement being formed of calcined magnesium oxide in the form of particle size distribution range averaging about 10-12 microns and present in the ratio of 1.5-3 parts by weight calcined magnesium oxide to 3 parts by weight magnesium sulphate, the cement being present in the ratio of 1.5-6 parts by weight cement to one part by weight glass fibers.

13. An article of manufacture comprising a porous, board-like member consisting essentially of glass fibers bonded with a magnesium oxysulphate cement containing a wetting agent selected from the group consisting of alkyl, aryl, and mixed alkyl aryl sulfonates, and alkali metal salts thereof, fatty acid amines, fatty acid esters, polyglycol ethers, polyglycol esters, fatty acid esters of higher alcohols and ethylene oxide condensates of fatty acids, the magnesium oxysulphate par ticles having a bulk density of about 55 pounds per cubic foot and present in the ratio to 1.5-3 parts by weight calciued magnesium oxide to 3 parts by weight magnesium sulphate, the cement being present in the ratio of 1.5-6 parts by weight cement to one part by weight glass fibers.

' 14.` The method as claimed in claim 8 in which the wetting agent is a compound selected from the group consisting of alkyl, aryl, and mixed alkyl aryl sulfonates and their water soluble salts, fatty acid esters of higher alcohols, and ethylene oxide condensates of fatty acids.

References Cited in the le of this patent UNITED STATES PATENTS OTHER REFERENCES The Condensed Chemical Dictionary, 3rd ed. Reinhold Pub'. Co. 1942, pp. 173-174.

Plastic Magnesia Cements, The Dow Chemical Co. 1927, pgs. 66 and 67. 

1. AN ARTICLE OF MANUFACTURE COMPRISING A POROUS HARD, BOARD-LIKE MEMBER CONSISTING ESSENTIALLY OF GLASS FIBERS BONDED WITH AN INORGANIC CEMENT SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM OXYCHLORIDE AND MAGNESIUM OXYSULPHATE AND PRESENT IN THE RATIO OF 1 PART BY WEIGHT GLASS FIBERS TO 1.5-6 PARTS BY WEIGHT CEMENT.
 5. THE METHOD OF MANUFACTURING A POROUS STRUCTURAL BOARD COMPRISING THE STEPS OF APPLYING A SLURRY OF A CEMENT COMPSOITION SELECTED OF THE GROUP CONSISTING OF MAGNESIUM OXYCHLORIDE AND MAGNESIUM OXYSULPHATE IN EXCESS OF AN AMOUNT THAT IS DESIRES TO HAVE REMAIN IN THE BOARD ONTO ONE WALL OF A POROUS GLASS FIBER MASS, DRAWING OFF THE SLURRY IN EXCESS OF THAT TO PROVIDE 1.5-6 PARTS BY WEIGHT CEMENT TO ONE PART BY WEIGHT GLASS FIBER THROUGH AN OPPOSITE WALL, AND THEN SETTING THE CEMENT THAT REMAINS DISTRIBUTED WITH THE GLASS FIBERS. 